Fluorocarbon triazine compounds

ABSTRACT

1. A COMPOUND OF THE FORMULA   2-(X(M)-SI(-R(3-M))-CH2-CH2-(CF2)N-),4-RF,6-(X(M)-SI(-R3)-   CH2-CH2-(CF2)N-)-S-TRIAZINE   WHERE R1 IS A POLYFLUORINATED ALKYL RADICAL OF NO MORE THAN 12 CARBON ATOMS, X IS A HYDROGEN ATOM, THE HYDROXY GROUP OR A HYDROLYZABLE GROUP, R IS A MONOVALENT HYDROCARBON RADICAL OF NO MORE THAN 30 CARBON ATOMS OR A ACH2CH2- RADICAL IN WHICH A IS A PERFLUOROALKYL RADICAL OF NO MORE THAN 10 CARBON ATOMS; N HAS A VALUE OF FROM 1 TO 10 INCLUSIVE, AND M HAS A VALUE OF FROM 1 TO 3 INCLUSIVE.

United States Patent Oflice 3,847,916 Patented Nov. 12, 1974 3,847,916FLUOROCARBON TRIAZINE COMPOUNDS Yung Ki Kim and Ogden R. Pierce,Midland, Mich., assignors to Dow Corning Corporation, Midland, Mich. NoDrawing. Original application June 13, 1968, Ser. No. 733,833, nowPatent No. 3,532,696, dated Oct. 6,-1970. Divided and this applicationApr. 3, 1970, Ser. No.

Int. 'Cl. C07d 55/50 US. Cl. 260-248 CS 3 Claims ABSTRACT OF THEDISCLOSURE The invention provides triazines of the formula in which R,is a polyfluorinated alkyl radical of no more than 12 carbon atoms and nhas a value of from 1 to 10 inclusive. Fluoroalkylenetriazinescontaining silanes, silanols and siloxanes are disclosed as fluids,resins and elastomers.

The invention herein described was made in the course of, or under, acontract or subcontract thereunder, with the United States Air Force.

This application is a division of application Ser. No. 733,833, filedJune 13, 1968, now US. Pat. 3,532,696.

In one aspect the invention relates to vinyl perfluorocarbon triazines.In another aspect the invention relates to polyfluorinated hydrocarbontriazine-containing silanes and silanols. Further, the invention relatesto siloxane polymers containing triazine groups.

According to the invention, there are provided triazine compounds of theformula:

c112=on oFz).-o o orz .,c:a=om lk H I R! where R, is a polyfluorinatedalkyl radical of no more than 12 carbon atoms and n has a value of from1 to 10 inclusive.

R, can be any suitable monovalent fluoroalkyl radical, such as,perfluoroalkyls, for example, trifluoromethyl, iso(heptafluoropropyl),perfluoroisobutyl, perfluorooctyl and perfiuorodecyl. Also included aremonovalent hydrocarbon radicals partially substituted with fluorine suchas trifluoroethyl and 3,3,3-trifluoropropyl and radicals containingbromine or chlorine such as bromodifluoromethyl, chlorodifluoromethyland chlorodifluoroethyl. R; is preferably a trifluoromethyl radical. Thepresence of small amounts of fluoroolefinic radicals providescrosslinking sites in polymers of the above-described triazines.

The triazines of the invention can be prepared by the ammonolysis ofvinyl perfluorocarbon nitriles to obtain the corresponding amidinefollowed by acylation and ring closure utilizing a fluorocarbon acidanhydride to give the divinyl perfluorocarbon triazine structure. Thereaction is as follows:

Ammonolysis is carried out at low temperatures, for

example, C., while the acylation proceeds at higher temperatures (0 to+40 C.) in the presence of excess anhydride.

The preparation of the alpha-vinyl, omega-nitrile perfluoroalkane isaccomplished by reacting ethylene with an omega-bromoperfluoroester,Br(CF ),,COOR, in the presence of free radical catalysts, such asperoxides. The reaction is conveniently carried out at a temperaturefrom to C. under 25 to 50 p.s.i. pressure. The product from the additionof one ethylene group to the ester is dehydrohalogenated by reactionwith an alkali metal alkoxide in alcohol solvent. In carrying out thereaction, the alkoxide of the alcohol corresponding to the R group inthe ester is employed and the same alcohol should be used as thesolvent.

The nitrile is prepared by conventional reactions from the ester. Theester is hydrolyzed to the acid which is then ammonolyzed to produce theamide, CH =CH(CF ),,CONH The amide can be dehydrated by conventionaldehydrating agents, such as P 0 or phosphorous pentachloride to obtainThis reaction is described in detail in my copending application Ser.No. 598,604, filed Dec. 2, 1966, now US. Pat. 3,503,945.

Examples of the triazine compounds of the invention include thefollowing:

N CHz=CH(CFz)a([3 fil(CFz)3CH=CH2 provided organosilane andorganosilanol compounds of the formula:

wher e 'X is a hydrogen atom, the hydroxyl group or a hydr ol y zabl'e"group, R is' a monovalent hydrocarbon radical or a AcH CH -radical inwhich A is a perfluoroalkyl radical, R is as defined hereinbefore, n hasa value of from 1 to 10 inclusive, m has a value of to 3 inclusive. Theterm hydrolyzable group means that the group is removed from the Si atomby reaction with water at room temperature. As described above, X can beany hydrolyzable group such as halogen atoms; such as fluorine, chlorineor bromine; hydrocarbonoxy groups such as methoxy, ethoxy, octadecyloxy,allyloxy, cyclohexyloky', phenony, tolyloxy, benzyloxy,

. CH3) OCHzCHzOCHs and (OCHz CH 002115;

acyloxy groups such as acetoxy, propionyloxy, benzoyloxy,cyclohexoyloxy, and

ketoxime groups such as -ON=C(CH and amine groups such as NH N(CH andsulfide groups such as SCH and the nitrile groups, the isocyanate group,sulfate groups such as --O O CzHr;

sulfonate groups such as carbamate groups such as OOCNHCH OOCN(CH 2 a rz21, (0P CF- and C F30 F20 F The above described organosilanes andsilanols (H) are best prepared by reacting silanes of the formula xmsiHRS-m with the previously described triazines of the formula (1) Thisreaction is carried out in the presence of an excess" of platinumcatalyst, such as chloroplatim'c acid, in the conventional manner foradding SiH compounds to compounds having the terminal CH =CH group.

The silanols of the invention (i.e. wherein X is -OH) can be prepared byhydrolyzing the corresponding hydrolyzable silane under neutralconditions by any of the well-known methods such as hydrolysis of thosecompounds in which X is methoxy.

When R is an alkenyl radical in the silane of the invention, the R groupis added to the Si atom by reaction with a Grignard reagent, RMgX, afterthe vinyl addition reaction.

Examples of the above defined compositions includez Thirdly, theinvention provides siloxanes having at least one unit of the formula inwhich R, R, and n are as described before and each 0'. independently hasa value of from 0 to 2 inclusive, any remaining units in the siloxanebeing of the formula in which Z is a hydrocarbon or halohydrocarbonradical, or X group and b has a value of from 0 to 3 inclusive.

The siloxanes of the invention can be prepared by two methods. First isby the hydrolysis or cohydrolysis of the above defined silanes (II), byconventional means, or by cohydrolysis of the defined silanes (II) withsilanes of the formula Z SiX in which Z, X and b are as defined above.The particular method chosen for hydrolysis or cohydrolysis can varydepending upon the nature of the substituent groups on the silicon.There are no critical conditions other than those for hydrolyzing andcohydrolyzing silanes.

The second method of preparing such siloxanes is by the addition ofsiloxanes containing SiH groups to the divinyl triazines (I) of theinvention in the presence of platinum catalysts. The conditions forcarrying out this reaction are those normally employed for the additionof SiI-I- containing silloxanes to olefins.

As can be seen the siloxanes of the invention can be homopolymers orcopolymers of various types of triazinecontaining siloxane units. Inaddition the siloxanes can contain siloxane units of the formula inwhich b has a value of from to 3 inclusive. Thus, included are units ofthe type SiO ZSiO Z SiO and Z SiO Z can be a hydrogen atom, any of theabove defined X groups or any hydrocarbon radical, such as themonovalent radicals specifically shown for R; divalent hydrocarbonradicals such as alkylene radicals, for example, methylene, dimethylene,trimethylene or tetramethylene; arylene radicals, for example,phenylene, xenylene, tolylene, xylylene or naphthylene; cycloalkyleneradicals, for example, cyclohexylene and cyclopentylene; and alkeuylradicals, for example, vinyl, allyl, hexenyl and butadienyl.

Z can also be any halohydrocarbon radical such as chloromethyl,gamma-chloropropyl, bromo-octadecyl, chlorocyclohexyl,bromocyclohexenyl, 3-chlorobutenyl-4, chlorophenyl, bromoxenyl,4,4,4-trifluorooctyl, tetrachlorophenyl, p-chlorobenzyl,3,3,3-trifluoropropyl and 1o 24 2 2- The siloxanes of the invention arefluids, resins and elastomers. The elastomers are especially useful assealants where a wide range of temperature stability and chemicalinertness are required.

The following examples are illustrative of the compositions of theinvention and should not be construed as unduly limiting the invention,which is properly delineated in the appended claims.

EXAMPLE 1 A mixture of 162.0 g. (1.06 moles) of CH =CHCF CF CN and 9.4g. (0.55 mole) of dry ammonia in 250 ml. of dry methylene chloride wasstirred slowly at room temperature for 8 hours under a coolingcondenser. The reaction mixture was kept at room temperature for 36hours without stirring and was then added slowly into a stirred mixtureof 290.0 g. (1.38 moles) of trifluoroacetic anhydride and 400 ml. of drymethylene chloride at 0 to C. This mixture was kept at room-temperaturefor 18 hours and then poured into twice its volume of ice cold water.The methylene chloride layer was separated, washed with water, and driedover Drierite.

After evaporation of methylene chloride, the resulting product wasdistilled to yield 160.0 g. (72.8% yield) of the pure divinyltriazine,B1. 110 to 111 C. (22 mm.), 1: 1.3785. The molecular weight by massspectroscopy was found to be 401 (cal. 401). The elemental analysis, Fand H resonance, and infrared spectral properties showed the structureto be 6 EXAMPLE 2 Into a stirred mixture of g. (0.223 mole) of OH =CHCFCF C CCF2CF2CH=CH2 1 I JFK n 1.4050. The elemental analysis and spectralproperties (F and H n.m.r. and LR.) were consistent with the diadduct.

EXAMPLE 3 Utilizing the method of Example 2, about 16 hours of reflux ofa solution of (1.5 g., 0.0037 mole),3,3,3-trifluoropropylmethylchlorosilaue (2.0 g., 0.011 mole) and 50 ,ul.of 0.1 M solution of chloroplatinic acid in isopropyl alcohol gave 45%yield of About 29 hours of gamma-irradiation (1.6 Mrad per hour at C.)of a solution containing 5.0 g. (0.013 mole) of N CH =CHCF CF -CCCFzCF2CH=CHz N 1 0 11 3 and 7.6 g. (0.043 mole) of3,3,3-trifluoropropylmethy1- chlorosilane gave EXAMPLE Fourteen games ofin 70 m1. of ether were added to 120 ml. of saturated aqueous sodiumbicarbonate solution while stirring at room-temperature. After stirringfor 1.5 hours, the ether solution was separated, washed with 5% aqueoussodium chloride solution, and dried over Drierite. After evaporation ofether under vacuum the resulting viscous liquid product was placed undervacuum at room-temperature for 24 hours to remove volatile materialssuch as solvents. A yield 13 g. of

was obtained. The molecular weight by the vapor phase osmometry wasfound to be 795 (calcd. 717), and the hydroxy content was found to be4.52% (calcd. 4.74%). The spectral data were in agreement with the diolstructure.

EXAMPLE 6 A mixture of 19 g. of

and 5 drops of tetramethylguanidine-trifluoroacetic acid solution washeated while mixing by rotation at 70 to 75 C. under -15 mm. Hg for 27hours, at 80 C. un-

der 0.3 mm. Hg for 16 hours, and then at 100 C. un-

der 0.2 mm. Hg for 45 minutes. The resulting polymer was 17.5 g. ofrubbery gum having the structure shown The polymerization catalyst(tetramethylguanidinetrifluoroacetic acid solution) was removed from therubbery polymer in the following manner: The polymer was dissolved inisopropyl acetate, treated with acidic synthetic resin, Washed withWater, and dried over Drierite. Evaporation of isopropyl acetate gavethe catalyst-free rubbery gum.

8 EXAMPLE 7- A mixture of 25.0 g. (0.0624 mole) of N\ /N C 5F.

19.4 g. (0.0650 mole) of CH3 CH3 HS OSiH,

Ha Ha CH2 H2 CF: CFa

EXAMPLE 8 a The ultraviolet irradiation of an equimolar mixture of C JFaand CH1: CH3

H S i-O- H1 in the presence of a catalytic amount of di-t-butylperoxideresulted in a viscous liquid product at the end of 13 days.

A viscous liquid product was obtained from N w CHFCHGF CFQ-(i)ficmomothom and ma CH3 HSi0-iH OF: Fa

by similar methods.

EXAMPLE 9 When 50 mol percent of cm N om I I CISICH CHflCFgh-l?(I3(CF:)zCH2OH2Sl1C1 Hz N OH: I I CH2 (3H2 CF; CH2 CFS is cohydrolyzedwith 25 mol percent (CH SiCl and 25 mol percent of C H SiCl in thepresence of water, the following copolymer is obtained: 50 mol percentof 25 mol percent of (CH SiO units and 25 mol percent of C H5SiO units.

EXAMPLE When 50 mole percent of the triazine-containing silane used inExample 9 is cohydrolyzed with 50 mole percent (CH SiCl a fluidcopolymer having the following composition is obtained: 50 mole percentCH3 N CH 10 SiCHzCH2(CF2)2C C(CF2)2OH2CH2iO1/2, CH2 N N CH2 CH2 0/ CH2CFa :112 CFK and 50 mole percent (CH SiO units.

EXAMPLE 11 When is reacted with CH =CHCH MgCL the following compositionis obtained:

10 Hydrolysis of this silane produces a siloxane which is readilyvulcanized.

That which is claimed is: 1. A compound of the formula R; is apolyfluorinated alkyl radical of no more than 12 carbon atoms,

X is a hydrogen atom, the hydroxy group or a hydrolyzable group,

R is a monovalent hydrocarbon radical of no more than 30 carbon atoms ora ACH CH radical in which A is a perfluoroalkyl radical of no more than10 carbon atoms;

n has a value of from 1 to 10 inclusive, and

m has a value of from 1 to 3 inclusive.

2.. A compound in accordance with claim 1 wherein J OHN M. FORD, PrimaryExaminer U.S. c1. X.R. 26046.5 E, 78, 566R

1. A COMPOUND OF THE FORMULA 